Process for breaking petroleum emulsions



V YUNIT Patented Dec. 10,1935 7 nmmarficqnotiicm e ;:-EMU .Q 3 i ".iClaudius? H. Mi signor'to'lre Mo., a corpora Y Application nc'iiibi7,1933; Serial'NoflZQLM] YY Y Y l Qlairns (cr me- .4) relates to thetreatingntpmhii i an wate u has petroleum ,separatingfthef oil 1 rltooi-issiRob'eits, Marine;-

tolite Company,.=.Webste1-, Groves,

tion =of Missouri; i

' pre ar This-invention sions of mineral o emulsions, for the purpose offrom the water; 1 Petroleum emulsions type, and comprise fi curringwaters, or brl less permanent state t constitutes the con .They areobtained from producing the bottom of oil storage monly referred to ascut 01 fied oil, and bottom settlings. The object of my and inexpensiveprocess ior'sep of the'character referred to intoith'ei parts of'oil andwater or brine; 'Briefiy described, 'jecting a'petroleum type to theaction of a tre "sifying agent of the kin are of ,the water-in oil letsof naturally-oces dis rsed i m iei rv hroughout theioil which 1? theemulsion, wells and from j'agent 'cbnt m ila 'mixed-este' Y M y Y abine'd' W'ith'the*polyhydricalcohol or re:sig:iu.e=is;'de {Tired rrp'mjnonhidroxylated; detergentrimming,v

tinuous phaseo invention is: to provi aratingemulsions a a l I*potas'hto Iform soaps ror-detergents; It '1s-:,also- M myDIOCGSSLCOIISI Y Y emulsion of the water inso'il ating agent ordemulhereinafter described, lsion to break down and t parts of 'oilandwater acids thereby causing the'emu ate intoitscomponen the emulsionis permitted: to reor brine, when Y er treatment, or is main in aquiescent state aft subjected to other equiyalent separatoryprocedemulsifying agentused amixed ester of aIpol'y o: the kind obtainedlcohol or alcohols or derivaform miked type estersgwith ids, one beingfadetertreating agent or 7 in my process consi hydric alcohol or a when apolyhydrica tives thereof unite to two dissimilar carboxy as h bth b i aa d furthermoraiwith r i u b m a ca b xygac di catlon't'hatatleasttwopolyhyls attached to the-sameor Y lcohol molecules or residuesolybasic carboxy 'acid gent-forming carboxy aci a polybasic c the addedquahfi dric alcohol hydroxy different polyhydric' 'a be replaced by thesame p arboxy acid, ,an

Sald treating ag resents one sub-division o terials' contemplated; ofthe process 'describ -tion forpatent S 19,33,'and is "also 1' row classof materials co treating "agent pending application;

fiIedDecemb'er 7, 1 lent and. not claime lng applications. Esters areobtaine hols, such a's'monohydric or eluding monob'asic or andQOOH istheconventional carboxylgroupr Y .r 'rnmiw, said j eo-nendingapplication SeriaL'No of 'the ,process for atent Se i pecifica l d fier:(1 per se in either-o e esteriflc olyhydric alcohols, I 7 YreSu1tli1g'8St8r mixed'ester. .The treating hydrokylated' fa ty; acidssuch as. oloeic acid} stearic acid, palmitic acid, linoleicacid, etacomein with' alkalis-s'uch as caustic sodafor caustic known'that'non-hydroylated, monoca rbox y rosin acids -f-such as abietic" acid; combine?with, alkfato pr'oduce detergent "material; "Naphthenic I ordetergentsl' The expression ffnon hydroxylatv "ed" detergent-forming,inonocarboxy acids refers "to the a type of materials above indicated.The, I

fpolyhydric alcohol employed. to producethe treat; 2 Y "f, in a"gent'i1sed in my process must IIOt' Qn Iy L be I: Y *combinedwith atleastrone moleculeoianon-hydroxlated, detergent-forming onocarbogy,acid,- but itmust also. be ,combinedylith at least 1 on'e' molecule "of,a gpolybasic acid, 1 and-furthere *hior', withthe-"addedqualification-that,atdeast t wo;bblyhydricalcoholhydroxyls.at'fiachedto-the. 1 1

'sar'n''ordifferent polyhydric alcohol molecules or I that if a atrihydric; alcohol; such glycerol: 15 v combinedjlwi'th'a d'ibasic acid,such as; succinic 1 acidfahd (also. with the mdnqca'rbox detergent-r;

I forming-acid such'a's oleicacidgsoj that complete f ationresultsj,'then the finishedpmdut xpressed'ilbyjthe. iormula D.K:R"'jin;. Y the lOlyhydric"alcohol residu is ed by my process'l consists of a petroleumare 'generally nonf'h ydrox lated and monocarboxylicgand theycom-f I :7"bine withalkalies togproducesoap-like materials may denote apolyhydric, alcohol he 1 "famine RWOHM, in which nnrepresents,,.the"numeraltwo, orlm'orei (Apol basic, carboxyacid Y my be denotdbytherormma,Aiecoornu 1 which} represents'ith'e numeral two; or more;;.

Qforming acids herein contemplated" may, be rep,"

esentedj'byfthe formula'DCOOH, m mcnpin representsf the characteristichydrocarbontchainfi and if the glycol isifirst combined with an oleicacid and, then combined withsuccinic acid, it isv obvious that amixeda'cid ester, must result, in-

sofar th'at t'he mixedester'containsan uncom- 'bined: carboxyl radical.Such a. type of mixed ester may be designated by the formula] D.A.(COOH)R, in which iorm'ula the symbols have 7 their previous significance andt v I presents the numeral one or more. "If glycerol s replaced bydiglycerol, which is an;ether, alcohol,,havi' four hydroxyls, and if arrioleofz-oleicacidand mole of succinic acid be combined therewith; the

mixed ester thus resulting would contain hydroxyl I and the material i,of, th1

,carboxyli,of'gsuccinic ing hydroxyls of the sa an amphoterica. mixeD.A.(COQH)':R. OH

neutral esterQcirb'as esters described above, maybe i 1 resents thenumeral zero or one o case-residual hydrOxYl radicalsm 'h with any-.1suitable-facids such "In the present process n treating agent ordemulsify g agent'ha i general characteristicaoiran-mixed ve 'ing' theadditionalr qualifica same *orfditferent. p olyhydric a'lcolio Iresidues mustibeuteplaced bythe sa me p carboxy acidresiduel;Forinstanca'ifpne,re ,ts

acid so that eSterificati complete,

hen reacts -a'{ mole of. oleic acidthe 1 ouslyformed ester, one thenobtains a compound which maybe represented-by; the, type formula D.A R.;in which D isithe detergent-for m'rmma' employs. acolonbetweenlg a n toin- I "dicate tha-t'the twovalencesof thegradicalR' a j-satisfiedby thedibasic acid resid productis amixed ester of the kin eutral' 'in*the sense that the mixed ltains no residual -carboxyll or hydrox Howev'en ifone combined oleic. acid wi line so as to'iprojduce mono T y termed themonovqlein vwithu a tricarboxy' acid such" as 'citric :acid rsothat thetwo I glycerol hydroxyls are replaced b th acid residue; and so thatthere" is boxyL theni the mixed esters o af which 'the lsymb olsehave kcancenuLikewise, if one ,com 1 glycerolto'give onemole of d i glycer olI 1 an ether alcohol vingffour alcoho c'h by the-formula acterized bythe formula DQAzRIOHh, which ,the symbols have their previoussignificance.

*In the previous case'onewould have an acidic mixed ester and in thislattercase one Obtains a. basic mixed ester.

Similarly, if diglycerol were one mole of I oleic acid and .then moleofqcitric acid, d ester of the type one w :p,( COOH)i.A:R.(OH)t. Thislatter would rep-' resent an axnphoterictype of mixed ester. It

shoul mike ester is neutral, acidic, basic, or ampho tferic,-th a' ja sttwocarbcxyls of the polyhydric replaced by the same ,polyunite with twon oles of ethylene"g1yco1, and if e'mole ofbleic acid' be combinedtherewitliby niting with one "of the remaining hydroxyl s, en the 'n'aterial thus obtained may' be dicated residue 1i$"replaced" :two 1 1polyhydric alcohol yhydroxyls but I said-two hydroxyls: wereattachrad-to1 two difiertype will be referred to as cyclic.

,nonvcyclic is condensed or resinified I 9 3 97 placed two hydroxyls ofthe same polyhydric alto cohol. In. the last class of mixedester's'described the polybasic acid residue replaces two hydroxyls notattached to the same polyhydric alcohol'residue. Since there is acertain cyclic-structure between Aand Rin the former class, said formerv The word cyclic" is not used in its ordinary signif cance, butsimplywith this specific significance.- The latter type of materialswhich have been'described will be characterized'as' non-cyclic.Hcreag'ain used in its peculiar obvious significance, and not in amannerusually employed in organic chemistry. ,Variou's polyhydric a100- holsmay be employed. They maybe aliphatic, aromatic, cyclic, aralkyl,heterocyc lic. "etc; Suitable polyhydric alcohols includeethyleneglycol, glycerol, erythritoi adohitoLfmanhitoi,'dih'ydroxy-naphthalene,alizarin, purpurin, te'rpin,dihydroxy-thiophe'ne, 'etc. Simple derivatives of the alcohols, suchaschloro-giycerol, ether alcohols, polyeglycol's, poly-glycerois, etc. maybe "as effective as the unaltered polyhydric alcoholsf Likewise, one'mayemploy various polybasic carboxyacids, including those ofthe aromatictype, alkyl type, aralkyl type, cyclic type, heterocyclic type, etc.Suitable examples including those previously pointed outare succinic,maieic, malic, aconitic, tartaric, citric, fumaric, tricarballylic, Itrihydroxy glutaric, mesoxalic, phthalic,

oxalic,:d iphenic, naphthali c, benz'oyl benzoic; trimesic, meliitic,cinchomeronic, quinolinic, camphoric, aspartic, norpinic, glutamic, etc.O ne"may use the-anhydrides instead of the acidstherr'rselves, or onevma'yuse the simple derivatives thereof; In addition, the polyh'ydroxyphenols,

. which areamphoteric in nature, such as catechol,

pyrogallol, hexahydroxyresorcinch quinol,

and are equiva phenol, etc., may be employed as lent to polybasic;carboxyacidswhen caused to react with more basic substances or areequivalent to polyhydric alcohols when caused to react with more acidicsubstances than themselves.

As previously indicated, D'COOI-I is a non-hydroxylated, monocarboxy,detergent-forming acid, such as oleic acid, stearic acid, palmitic acid,abietic acid, naphthenic acid, etc. It is understood that the simplederivatives of these acids, such as the chlorine derivatives, may beused instead of the acids themselves.

The manufacture of mixed esters is relativelysimple. Generally speaking,the reagents are heated together under conditions which tend to removethe waterformed as a result of esterification. In some instances thereagents are'heated at a temperature higher than the boiling point ofwater. Sometimes esterification is carried on at a temperature lowerthanthe boiling pointof water, and a dried inert gas is passed'through themixed mass to eliminate any water which may be formed. Sometimes acatalyst, such as a trace of a mineral acid is added. These processesare well known and have been employed in the production of syntheticfats, neutral gums, plasticizers, synthetic resins, perfume materials,"

flavoring materials, etc.

It is also well knownthat complex organic molecules of the kindconstituting the type of reagent contemplated herein for use in myprocess, exhibit a marked tendency to polymerize, condense or resinify.Such. complex polymerized,

products are just as suitable for use as the demulsifying agent in myprocess as the simpler unpolymerized, uncondensed 'or non-resinousproducts and the claims attached types without differentiation. i

If the reactionresults in the formation of an amphoteric or acid" mixed:ester; then obviously the 'acidichydrogen canbe replaced byany equiv;-alent.* Such acidic material may vbe treated with a suitable alkalinemateriahsuch as caustic soda,

caustic potash, ammonium hydroxide calcium hydroxide,- magnesiumhydroxida' etd, so as to produce the correspondingmetallic, salts,,manyof this specification areintended to include allwhich'arewater-soluble; The ammonium radical is considered as ametal:Basicqamines, such. as

triethanolamine;aniline; etc. may be employed {or neutralization;Theiacidic hydrogen maybecombined with an alcohol. of any kind, such as;ethyl,

methyl, propyl alcohols; etc.- to producean ester. The acidichydrogen-may. remain unneutralized.

The hydroxyl of the: carboxyl jmay bey combined withanaminebyeiiminating a: hydrogen of the Water-soluble salts ofthekind'previously'referred U amine with the separation of a molecule of,yvate'r.

to 3 may beireacted with metallic. .waterj-soluble' salts, such ascopper salts, ironsaltsgaluminum "salts, zinc salts, magnesium salts,etc. ,tol pro- Y B0 Inthese last mentioned type formulas the hydrogen'of the carboxyl, H, is replaced by Z, which" indicates an acid hydrogenequivalent of the kind described, or may mean the acid hydrogen itself,

taken place, i. e.,.until there is no residual car-.

boxylichydrogen. The resultant basiciproduct', I due to the residualhydroxyl; is combined with one-mole (or 282 lbs.) of oleic acid, byheating,

'until the acidity of the carboxylichydrogen of the oleic acid hasdisappeared. The finished product may be indicated by the formula D.A:R,inwhich D is anoleic acid residue, A-isa phthaiic' acid'residue and R isa glycerol residue, and

, characterized by the fact that two of the glycerol Y hyd'roxyls havebeen replaced by a single phthalic T v anhydride residue; Mono-oleinisthe product obtained by neutralization of one hydroxyl of a I moleofglycerol by a mole of oieicacid. Phthalic 25 The previously describedtypes of materials 1 acid may be considered as $9. phthal-yl radicalC6H4(C0)2 "plus two hydroxy radicals. i If ;one considers mono-olein aslosing. two 1 hydrogen atoms in the hydroxyl position, and a phthalylradical being substituted therefor, one can refer to thepreierred-reagentejusts described asy-being neutral phthalyrmono-oleincThe materials previously desc'ribed need not be employed alone, asademulsiiyingage'nt, but may be employed in conjunction with othersuitable 'deniulsifiers, such as waterwsofteners, modified fatty acids,oil-soluble or-water-soluble petroleum sulfonic acids, substitutedaromatic sulfonic acids,

dialkyl" sulfo acidsysubstituted vamine acidic bodies, etcL', or thesalts and esters of thesame ;or the like. One Jmay' add any s uitable.inert solvent or solvents to the reagent contemplated, particularlysolvents .whichwould lower the vis- -cosity ofthe product and make it'more, adaptable I J pine oil, ethyl alcohol, butyl alcohol;propylalcoiforuse, such as kerosene, solvent naphtha, cresol,

ho], benzol," etc. I I

In practicing my process,:a treating agent or demulsifying agent ofthe-kindfabove described may'b'e brought in contact with the emulsion tobetreated in any of :the numefrous, waysnow employed in the treatment ofpetroleum emulsions of the water in ollfiypb w Chemical mulsifyingagents, such, for example,- as by inf troducing the treating age'nt intothe .well in which the emulsion is produced, introducing the treatingagent into a conduit through whichthe emulsion is flowing, introducingthe treatingagent into a tank in which the emulsion is stored, orintroducing the treating agent, into a container that holds a sludgeobtained from the bottom of an oil storage tank. In some instances, I

it "maybe advisable to introduce the treating agent into aproducing wellin such away that'- it will become mixed with water and, oil that areemergingtfromthe surrounding strata, before said water and oil enter thebarrel of the well pump or the tubing up through which said water aoaaeve centrifuges, orelectrical dehydrators.

olein.

and oilfiow to the surface of the ground. After treatment the emulsionis allowed wetland "in a quiescent state, usually in a settling" tank ata temperature varying from atmosphericftemperature to about 200 'F.,'soas tdpermitth water or brineto separate Iron; the oil,1t"beingpreferable to keep thetemperature low enoughfso as toprevent thevaluable constituents of theoil V -fro-m vfolatili'zingLflII desired'the treated eniul sionfmay be actedupon' by one or the other of 10various kinds of apparatus "now used in the operation of breakingpetroleum emulsions, such'as homogenizers, hay' tanks, gun "barrels,filters,

The amountof treating agent on the anhydrous basisthatis' -required tobreak the" emulsionmay vary from approximately 1 part0: treatingegentto' 500 parts of emulsiom 'upfto a ratlo or 1part of treatingfagent to20,000'parts"o f emulsion, depending upon the type or kind of emulsionbeing treated. In treating excepti'onally refractory emulsions of'th'ekindjcommonljreferredi to as v tank bottoms'f"or (residual 'pitoils, the minimum ratio above referred'to is often necessary,

butgin treating freshemulsions, it e., emulsions that will yield readilyto; the action of chemical demulsifyingj agents, the maximum ratio abovementioned will frequently, produce "highly satis- V factory results,Forthe'average petroleum'einul- 'sion Jof' the waterrin-oilfty pe aratio of l p'artgo of treating agent to 10,Q 0 0 p'arts o'f emulsionwill ,usually be found'to produce commercially satisfactory results; I Hg i Having thus describedmy'invention; what'I I claimas new anddesire'to secure by'Letters Pat- 1 A process for breakinga'petroleum-emulsion of the, water imoil type which eonsi s tsinsubjecting" the emulsion" to theiaction of a c l ernulsifying agentcomprising neutral phthalyl' monoenemas; H. RoBEn'rs.

